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The role of π-bonding is also subtle: for the given group 2 examples with ‘‘weak π-donor’’ halide or related ligands, π-bonding clearly favors the linear structures [77]. For more covalent transition-metal examples with strong donor ligands like ZrO2 , overlap of the π-type oxygen lp with an in-plane Zr d-orbital actually favors even more pronounced bending [72]. These aspects show up also for more complex heteroleptic complexes. Indeed, the ‘‘non-VSEPR’’ structures are not restricted to exotic dicoordinate species but extend also to higher coordination numbers.
Published 2014 by Wiley-VCH Verlag GmbH & Co. KGaA. 1 Overview of the structures of E2 H2 isomers A–E which are relevant for the discussion of the bonding situation. in roughly the same region of space, whereas the p valence AOs of higher row atoms are much more extended in space than the respective s valence AOs. This may cause substantial differences in the σ- and π-bonds between atoms of the first octal row and the heavier main-group elements. Kutzelnigg came to the conclusion that the difference between the spatial distribution of the s and p valence orbitals implies that single bonds between the first row elements are weak and multiple bonds are strong, whereas for the second or higher row elements, single bonds are strong and multiple bonds weak [7].
Phys. , 290, 488–494. 1 Introduction Chemical experience has shown that compounds with multiple bonds between heavier main-group atoms are much more difficult to synthesize, and that they often exhibit greatly different geometries than their counterparts of the first octal row [1]. The most prominent examples are the group-14 homologues of ethylene and acetylene. The chemical bonds in H2 C=CH2 and HC≡CH are archetypical examples for σ- and π-bonding in planar alkenes and linear alkynes. 1) [3]. Experimental evidence is in agreement with the theoretical predictions.